CN110214052B

CN110214052B - Particulate adsorbent material and method of making the same

Info

Publication number: CN110214052B
Application number: CN201780084258.6A
Authority: CN
Inventors: 蒂莫西·M·伯恩; 劳伦斯·H·希尔特齐克; 马尔塔·利昂·加西亚; 卡梅伦·汤姆森
Original assignee: Ingevity South Carolina LLC
Current assignee: Ingevity South Carolina LLC
Priority date: 2017-01-25
Filing date: 2017-07-21
Publication date: 2023-06-20
Anticipated expiration: 2037-07-21
Also published as: CA3049957A1; CN110214052A; EP3573752A1; KR20190092598A; JP2020506797A; KR20220159499A; KR102471433B1; JP2022166096A; KR20210107908A; JP7121018B2; US20180207611A1; EP3573752A4; BR112019015315A2; CA3049957C; MX2019008807A; KR102295334B1; KR102594825B1; WO2018140081A1; CN116870882A; BR112019015315B1

Abstract

The present disclosure describes a particulate adsorbent material comprising: an adsorbent having microscopic pores with a diameter <100nm, macroscopic pores with a diameter of 100nm or less, and a ratio of volume of macroscopic pores to volume of microscopic pores of greater than about 150%, wherein the particulate adsorbent material has a retention of about 1.0g/dL or less. A method of making a particulate adsorbent material comprising: mixing an adsorbent having microscopic pores with a diameter <100nm with a processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of +.100 ℃; and heating the mixture to about 100-1200 ℃ for about 0.25-24 hours, forming macroscopic pores having a diameter of less than or equal to 00nm when the processing aid sublimates, evaporates, chemically decomposes, dissolves or melts, wherein the ratio of the volume of macroscopic pores to the volume of microscopic pores is >150%.

Description

Particulate adsorbent material and method of making the same

Citation of related application

The present application claims priority from U.S. provisional application No. 62/450,480 filed on 25.1.2017, the contents of which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates generally to particulate adsorbent materials and methods of making the same. More particularly, the present invention relates to a particulate adsorbent material for use in evaporative fuel vapor emission control systems and a method of making the same.

Background

Vaporization of gasoline fuel from automotive fuel systems is a major potential source of hydrocarbon air pollution. Such emissions may be controlled by a canister system that uses activated carbon to adsorb fuel vapors generated by the fuel system. In certain engine operating modes, adsorbed fuel vapor is periodically removed from the activated carbon by purging the canister system with ambient air to desorb the fuel vapor from the activated carbon. The regenerated carbon may then adsorb additional fuel vapors.

The increase in environmental problems continues to drive the stringent regulations on hydrocarbon emissions of motor vehicles, even when the vehicle is not running. When the vehicle is parked, the vapor pressure in the vehicle fuel tank will increase as the ambient temperature increases. In general, in order to prevent fuel vapor from leaking from the vehicle to the atmosphere, the fuel tank is vented through a conduit to a canister containing a suitable fuel adsorbing material that can temporarily adsorb the fuel vapor. A mixture of fuel vapor and air from the fuel tank enters the canister through a fuel vapor inlet of the canister and expands or diffuses into the adsorbent volume, wherein the fuel vapor is adsorbed in a temporary storage area (temporary storage) and the purified air is released into the atmosphere through an exhaust port of the canister. Once the engine is started, ambient air is drawn into the canister system through the exhaust ports of the canister via the manifold vacuum. Purge air flows through the adsorbent volume within the canister and desorbs fuel vapor adsorbed on the adsorbent volume prior to entering the internal combustion engine through the fuel vapor purge conduit. The purge air does not desorb all of the fuel vapor adsorbed on the adsorbent volume, thereby producing residual hydrocarbons ("heel") that may be vented to the atmosphere. In addition, the heel, which is in partial equilibrium with the gas phase, also allows fuel vapors from the fuel tank to migrate through the canister system as emissions. Such emissions typically occur when the vehicle is parked and undergoes diurnal temperature changes over a period of days, commonly referred to as "diurnal ventilation loss (diurnal breathing losses)". The state of california low emission vehicle regulations dictate that for many vehicles starting in the model year 2003, these diurnal ventilation loss (DBL) emissions from the tank system should be below about 20mg ("PZEV") and for many vehicles starting in the model year 2004, below 50mg ("LEV-II"). Emission Test Program (BETP) for 2001 and following model motor vehicles, according to california evaporative emission standards and EPA control for 22 days 2012 and air pollution with motor vehicles written in test program: tier 3 motor vehicle emissions and fuel standards; the final regulations, 40CFR parts 79, 80, 85, etc., require tank DBL emissions not exceeding 20mg by the California low emission vehicle regulations (LEV-III) and EPATier 3 standards.

Various methods of reducing diurnal ventilation loss (DBL) emissions have been reported. One approach is to significantly increase the volume of purge gas to enhance the desorption of residual hydrocarbons followed by the adsorbent volume. However, this approach has the disadvantage of complicating the management of the fuel/air mixture during the purge step and of having a tendency to adversely affect the exhaust emissions. See U.S. patent No. 4,894,072.

Another approach is to design the canister to have a relatively low cross-sectional area on the venting side of the canister, either by re-sizing the existing canister or by installing an appropriately sized auxiliary venting side canister. The method reduces residual hydrocarbon heel by increasing the strength of the purge air. One disadvantage of this approach is that the relatively low cross-sectional area provides excessive flow restriction to the tank. See U.S. patent No. 5,957,114.

Another way to increase the purge efficiency is to heat the purge air, or have a portion of the adsorbent volume that adsorbs the fuel vapor, or both. However, this approach adds complexity to the control system management and causes some security problems. See U.S. patent nos. 6,098,601 and 6,279,548.

Another method is to direct fuel vapor through an initial adsorbent volume and then through at least one subsequent adsorbent volume prior to venting to the atmosphere, wherein the initial adsorbent volume has a higher adsorption capacity than the subsequent adsorbent volume. See U.S. patent No. RE38,844.

Along the concept of series adsorbents, the adsorbent volume has a rating of adsorption working capacity, with a specific range of gram-total working capacity towards the system exhaust, particularly useful for emission control tank systems operating at low purge volumes, such as "hybrid" vehicles, where the internal combustion engine is shut off almost half the time during vehicle operation, and where the purge frequency is well below normal. See WO 2014/059190 (PCT/US 2013/064407).

Another approach along the tandem adsorbent concept is to provide a specially shaped particulate adsorbent having a specific ratio of "macroscopic" pore volume to "microscopic" pore volume (similar to the macropore volume to the micropore volume) and having good adsorption/desorption properties, yet having lower flow restrictions, low level vapor retention of the adsorbent and sufficient strength. See U.S. patent No. 9,174,195. The method is further described for an emission control tank system wherein the target is an average pore size in the macroscopic size range. See U.S. patent No. 9,322,368. Both of these methods rely on a balance between shape, structural size and pore ratio properties to obtain adequate particle strength and adequate vapor desorption with the aim of reducing DBL emissions.

The common challenge and desire described by the above-described and other methods (see, e.g., U.S. patent No. 7,186,291 and U.S. patent No. 7,305,974) is to counteract the effect of residual adsorption vapor on tank system performance, particularly DBL emissions performance, where a high seek is made of the minimum amount of residual adsorption vapor (minimum amount of heel). In addition, it is also known that degradation of DBL emissions and working capacity performance of tank systems (also known as "aging") is caused by the accumulation of less scavengeable components in the adsorbed steam heel (see, e.g., SAE technical paper series 2000-01-895). Thus, the benefits of low hydrocarbon retention after purging are twofold: the DBL emissions levels of new vehicles are low and the operating capacity and emissions performance are maintained over the life of the vehicle.

While highly desirable as a method, the combination of low cost, low production complexity, high material structural strength, low flow restrictions, and minimum vapor retention for evaporative emission control created by particulate adsorbents is taught as a limited space. For example, as taught in U.S. patent No. 9,174,195, the useful range of macroscopic to microscopic pore volume ratios is limited to between 65% and 150% because mechanical strength fails at higher ratios. Further, vapor retention (retention) is asymptotic within the claimed pore ratio range, butane residual levels greater than 1g/dL as determined by standard ASTM tests, and greater than 1.7g/dL targets when the pore ratio exceeds the claimed 150% limit, in addition to poor strength.

Thus, there remains a need for a particulate adsorbent that is low cost, low in production complexity, has high material structural strength, has low flow restrictions, and has minimal vapor retention for evaporative emission control so as to have low diurnal ventilation loss (DBL) emissions performance and has the required operating capacity over the life of the vehicle.

Disclosure of Invention

Presently described are particulate adsorbent materials for evaporative emission control that have surprising and unexpected properties such as low retention (retention) and excellent strength. Accordingly, in one aspect of the specification, a particulate adsorbent material for evaporative emission control is provided. In general, the material comprises: an adsorbent having microscopic pores with a diameter of less than about 100 nm; macroscopic pores having a diameter of about 100nm or greater; and the ratio of the volume of macropores to the volume of micropores is greater than about 150%, wherein the retention of the particulate adsorbent material is about 1.0g/dL or less.

In some embodiments, the retention of the adsorbent is about 0.75g/dL or less.

In certain embodiments, the adsorbent has a retention of about 0.25 to about 1.00g/dL.

In further embodiments, the adsorbent is at least one of activated carbon, carbon charcoal (carbo-charcoal), molecular sieves, porous polymers, porous alumina, clay, porous silica, kaolin, zeolite, metal organic framework, titania, ceria, or combinations thereof.

In particular embodiments, the adsorbent has a micropore volume of about 0.5cc/g or less (about 225cc/L or less).

In some other embodiments, the adsorbent includes a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

In certain other embodiments, the three-dimensional low flow resistance shape or morphology is at least one of a substantially cylindrical body, a substantially oval prism (oval prism), a substantially sphere, a substantially cube, a substantially elliptical prism (eliptical prism), a substantially rectangular prism, a lobed prism, a three-dimensional spiral or helix, or a combination thereof.

In a further embodiment, the particle adsorbing material has a cross-sectional width of about 1mm to about 20mm.

In a certain embodiment, the cross-sectional width is about 4mm to about 8mm (e.g., about 5mm to about 8 mm).

In another embodiment, the adsorbent comprises at least one cavity in fluid communication with the outer surface of the adsorbent.

In other embodiments, the adsorbent is hollow in cross-section.

In one embodiment, the sorbent comprises at least one channel in fluid communication with at least one outer surface.

In certain further embodiments, each portion of the adsorbent has a thickness of about 3.0mm or less.

In one embodiment, the thickness of the at least one outer wall of the hollow shape is about 1.0mm or less.

In other embodiments, the hollow shape has at least one inner wall extending between the outer walls and having a thickness of about 1.0mm or less.

In particular embodiments, at least one of the inner wall, the outer wall, or a combination thereof has a thickness of about 1.0mm or less, about 0.75mm or less, about 0.6mm or less, about 0.5mm or less, or about 0.4mm or less.

In further embodiments, the thickness of at least one of the inner wall, the outer wall, or a combination thereof is from about 0.1mm to about 0.6mm, from about 0.1mm to about 0.4mm, or from about 0.1mm to about 0.3mm.

In some embodiments, the inner wall extends outwardly from the hollow of the particulate adsorbent material (such as from the center of the particulate adsorbent material) to the outer wall in at least two directions.

In some other embodiments, the inner wall extends outwardly from the hollow of the particulate adsorbent material (such as from the center of the particulate adsorbent material) to the outer wall in at least three directions.

In one embodiment, the inner wall extends outwardly from the hollow of the particulate adsorbent material (e.g., from the center of the particulate adsorbent material) to the outer wall in at least four directions.

In certain embodiments, the length of the adsorbent is from about 1mm to about 20mm.

In particular embodiments, the length is from about 2mm to about 8mm (e.g., the length is from about 3mm to about 7 mm).

In a further embodiment, the activated carbon is derived from at least one material selected from the group consisting of wood, wood dust (wood pit), wood flour, cotton linter, peat, coal, coconut, lignite, carbohydrate, petroleum pitch, petroleum coke, coal tar pitch, fruit pits (fruit pits), nut shells, nut pits, sawdust (sawpit), palm, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof.

In other embodiments, the particulate adsorbent further comprises at least one of the following: a pore forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves, or melts to form at least one void (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or more voids); an adhesive; a filler; or a combination thereof.

In a certain embodiment, the pore forming material or processing aid is a cellulose derivative.

In another embodiment, the pore forming material or processing aid is methylcellulose.

In one embodiment, the porogen or processing aid sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of about 125 ℃ to about 640 ℃.

In some further embodiments, the binder is a clay or silicate material.

In some embodiments, the clay is at least one of a zeolite clay, bentonite, montmorillonite clay, illite clay, french green clay (French Green clay), pasolite clay, redmond clay, terramin clay, activated clay (Living clay), fuller's Earth clay, orialite clay, vitalilite clay, rectorite clay (recterite clay), cordierite, kaolin, ball clay, or combinations thereof.

In a particular embodiment, the particulate adsorbent material has a packed bed pressure drop (pressure drop) of <40Pa/cm at an apparent linear air flow rate of 46 cm/s.

In another aspect, the present disclosure provides a method of preparing a particulate adsorbent material. The method comprises the following steps: mixing an adsorbent having microscopic pores with a diameter of less than about 100nm with a pore-forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to 100 ℃ or more; and heating the mixture to a temperature of about 100 ℃ to about 1200 ℃ for about 0.25 hours to about 24 hours to form macroscopic pores having a diameter of about 100nm or greater when the nuclear material sublimates, evaporates, chemically decomposes, dissolves, or melts, wherein the ratio of the volume of macroscopic pores to the volume of microscopic pores in the adsorbent is greater than 150%.

In some embodiments, the retention of the particulate adsorbent material is about 1.0g/dL or less.

In a further embodiment, the method further comprises extruding or compressing the mixture into a shaped structure.

In yet another embodiment, the adsorbent is at least one of activated carbon, molecular sieves, porous alumina, clay, porous silica, zeolite, metal organic framework, or combinations thereof.

In other embodiments, the mixture further comprises a binder.

In one embodiment, the binder is at least one of clay, silicate, or a combination thereof.

In a further embodiment, the mixture further comprises a filler.

In particular embodiments, the filler has a three-dimensional volume or shape or morphology.

In some other embodiments, the cross-sectional width of the adsorbent is in the range of about 1mm to about 20 mm.

In particular embodiments, the adsorbent includes a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

In one embodiment, the three-dimensional low flow resistance shape or morphology is a substantially cylindrical body, a substantially oval prism, a substantially spherical body, a substantially cubic body, a substantially elliptical prism, a substantially rectangular prism, a lobed prism, a three-dimensional spiral or helix, or a combination thereof.

In yet another embodiment, the adsorbent comprises at least one cavity or channel in fluid communication with an outer surface of the adsorbent.

In certain embodiments, the adsorbent is hollow in cross-section.

In particular embodiments, each portion of the adsorbent has a thickness of about 3.0mm or less.

In other embodiments, the thickness of the outer wall of the hollow shape is about 1.0mm or less.

In some embodiments, the hollow shape has an inner wall extending between outer walls.

In one embodiment, the thickness of the inner wall is about 1.0mm or less.

In another embodiment, the at least one inner wall, the at least one outer wall, or a combination thereof is about 1.0 or less, about 0.6mm or less, or about 0.4mm or less.

In yet another embodiment, the inner wall extends outwardly from the inner volume (such as from the hollow), such as the center, to the outer wall in at least two directions.

In yet further embodiments, the inner wall extends outwardly from the inner volume (such as from the hollow), such as the center, to the outer wall in at least three directions.

In certain embodiments, the inner wall extends outwardly from the inner volume (such as from the hollow), such as the center, to the outer wall in at least four directions.

In some embodiments, the length of the adsorbent is from about 1mm to about 20mm.

In certain embodiments, the adsorbent is about 2mm to about 8mm in length (e.g., about 3mm to about 7mm in length).

In a further aspect, the present disclosure provides a particulate adsorbent material produced by the method of the present disclosure.

The foregoing general field of use is given by way of example only and is not intended to limit the scope of the present disclosure and appended claims. Additional objects and advantages associated with the compositions, methods and processes of the present disclosure will be understood by those of ordinary skill in the art in light of the claims, specification and examples of the present invention. For example, the various aspects and embodiments of the disclosure may be used in a variety of combinations, all of which are expressly contemplated by the disclosure. These additional advantages, objects, and embodiments are expressly included within the scope of the present disclosure. Publications and other materials used herein to illuminate the background of the disclosure and in particular cases to provide additional details respecting the practice are incorporated by reference.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the disclosure and together with the description, serve to explain the principles of the disclosure. The drawings are only for purposes of illustrating embodiments of the disclosure and are not to be construed as limiting the disclosure. Other objects, features and advantages of the present disclosure will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate illustrative embodiments of the disclosure, in which:

FIGS. 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H1, 1H2, and 1I illustrate examples of alternative sorbent morphologies;

FIG. 2 is a graph of retention (g/dL) versus void ratio (i.e., the ratio of the volume of macroscopic pores of about 100nm or more to the volume of microscopic pores less than 100 nm);

FIG. 3 is a plot of 2mm strength versus void ratio (i.e., the ratio of the volume of macroscopic pores of about 100nm or greater to the volume of microscopic pores less than 100 nm);

FIG. 4 is a cross-sectional view of an apparatus for measuring the pressure drop generated by a particulate adsorbent; and

FIG. 5 is a graph of pressure drop (Pa/cm) at 40L/min versus nominal particle outer diameter (mm).

Detailed Description

The present disclosure will now be described more fully hereinafter, but not all embodiments of the disclosure are shown. While the disclosure has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications may be made to adapt a particular structure or material to the teachings of the disclosure without departing from the essential scope thereof.

The drawings attached hereto are for illustration purposes only. They are not intended to limit the embodiments of the present disclosure. In addition, the drawings are not drawn to scale. Common elements in the drawings may retain the same numerical designation.

Where a range of values is provided, it is understood that each intervening value, and any other or intervening value in that range, between the upper and lower limit of that range is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the range. Where a range includes one or both of the limits, ranges excluding both of those included limits are also included in the disclosure.

The following terms are used to describe the present disclosure. Where a term is not specifically defined herein, that term is given its art-recognized meaning by one of ordinary skill in the context of its application to describing the use of the present disclosure.

The articles "a" and "an" are used herein to refer to one or more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly dictates otherwise. For example, "an element" means one element or more than one element.

The phrase "and/or" as used in the specification and claims should be understood to mean "one or both" of the elements so joined, i.e., the elements are in some cases present in combination and in other cases present separately. The various elements listed with "and/or" should be interpreted in the same manner, i.e. "one or more" of the elements so joined. In addition to elements specifically identified by the "and/or" clause, other elements may optionally be present, whether related or unrelated to elements specifically identified. Thus, as a non-limiting example, reference to "a and/or B", when used in conjunction with an open language such as "comprising", may in one embodiment refer to a alone (optionally containing elements other than B); in another embodiment, it means only B (optionally including elements other than a); in yet another embodiment, a and B (optionally including other elements); etc.

As used in the specification and claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when items in a list are separated, "or" and/or "should be construed as inclusive, i.e., including at least one of the many elements or lists of elements, but also including more than one, and optionally additional items not listed. Only when a term is explicitly indicated to the contrary, such as, for example, "only one" or "exactly one" or "consisting of …" is used in the claims, will reference be made to comprising a number of elements or exactly one element in a list of elements. Generally, where an exclusive term (such as "any one," "one of," "only one of," or "exactly one of"), the term "or" as used herein should be interpreted to mean an exclusive substitution (i.e., "one or the other, but not both").

In the claims and in the above description, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "composition of," and the like are to be understood to be open-ended, i.e., to include, but not be limited to. Only the transitional phrase "consisting of … …" or "consisting essentially of … …" should be a closed or semi-closed transitional phrase, respectively, such as section 2111.03 of the U.S. patent office patent inspection program manual.

As used in the specification and in the claims, the phrase "at least one" when referring to a list of one or more elements is understood to mean at least one element selected from any one or more of the list of elements, but does not necessarily include at least one of each element specifically listed within the list of elements, and does not exclude any combination of elements in the list of elements. In addition to elements specifically identified in the list of elements to which the phrase "at least one" refers, this definition also allows for the optional presence of other elements, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of a and B" (or equivalently "at least one of a or B" or equivalently "at least one of a and/or B"), in one embodiment, may refer to at least one (optionally including more than one) a but not B (and optionally including elements other than B); in another embodiment, it means at least one (optionally including more than one) B but no a (and optionally including elements other than a); in yet another embodiment, it means at least one (optionally including more than one) a and at least one (optionally including more than one) B (and optionally including other elements); etc. It should also be understood that in any method claimed herein that includes more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited, unless explicitly stated to the contrary.

As used herein, the terms "gaseous" and "vapor" are used in a generic sense and are intended to be interchangeable unless the context indicates otherwise.

One aspect of the specification provides a particulate adsorbent material that can be used, for example, for evaporative emission control. Typically, the material comprises: an adsorbent having microscopic pores with a diameter of less than about 100 nm; macroscopic pores having a diameter of about 100nm or greater; and the ratio of the volume of macropores to the volume of micropores is greater than about 150%, wherein the retention of the particulate adsorbent material is about 1.0g/dL or less.

For example, the retention of the adsorbent may be about 0.75g/dL or less, about 0.50g/dL or less, or about 0.25g/dL or less. As a further example, the retention of the adsorbent may be about 0.25g/dL to about 1.00g/dL, about 0.25g/dL to about 0.75g/dL, about 0.25g/dL to about 0.50g/dL, about 0.50g/dL to about 1.00g/dL, about 0.50g/dL to about 0.75g/dL, or about 0.75g/dL to about 1.00g/dL.

In certain embodiments, the ratio of volumes is: at least about 160%, at least about 170%, at least about 180%, at least about 190%, at least about 200%, at least about 225%, at least 250, at least 275, at least 300, or at least about 350%. In other embodiments, the volume ratio is greater than about 150% to about 1000%, greater than about 150% to about 800%, greater than about 150% to about 600%, greater than about 150% to about 500%, greater than about 150% to about 400%, greater than about 150% to about 300%, greater than about 150% to about 200%, about 175% to about 1000%, about 175% to about 800%, about 175% to about 600%, about 175% to about 500%, about 175% to about 400%, about 175% to about 300%, about 175% to about 200%, about 200% to about 800%, about 200% to about 600%, about 200% to about 500%, about 200% to about 400%, about 200% to about 300%, about 300% to about 800%, about 300% to about 600%, about 300% to about 500%, about 300% to about 400%, about 400% to about 800%, about 400% to about 600%, about 400% to about 500%, about 500% to about 800%, about 500% to about 600%, or about 600% to about 800%.

The adsorbent may be activated carbon (which may be derived from at least one material selected from the group consisting of wood, wood chips, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit pits, nut shells, nut pits, sawdust, palm, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof), charcoal, molecular sieves, porous polymers, porous alumina, clay, porous silica, kaolin, zeolite, metal organic frameworks, titanium dioxide, ceria, or combinations thereof.

In particular embodiments, the adsorbent has a micropore volume of about 225cc/L or less (about 0.5cc/g or less). For example, the micropore volume may be less than or equal to about 200cc/L, less than or equal to about 175cc/L, less than or equal to about 150cc/L, less than or equal to about 125cc/L, less than or equal to about 100cc/L, less than or equal to about 75cc/L, less than or equal to about 50cc/L, or less than or equal to about 25cc/L. As a further example, the micropore volume may be from about 1.0cc/L to about 225cc/L, from about 1.0cc/L to about 200cc/L, from about 1.0cc/L to about 175cc/L, from about 1.0cc/L to about 150cc/L, from about 1.0cc/L to about 125cc/L, from about 1.0cc/L to about 100cc/L, from about 1.0cc/L to about 75cc/L, from about 1.0cc/L to about 50cc/L, from about 1.0cc/L to about 25cc/L, from about 25cc/L to about 225cc/L, from about 25cc/L to about 200cc/L, from about 25cc/L to about 175cc/L, from about 25cc/L to about 150cc/L, from about 25cc/L to about 125cc/L, from about 25cc/L to about 100cc/L, from about 25cc/L to about 75cc/L, from about 25cc/L to about 50cc/L, about 50cc/L to about 225cc/L, about 50cc/L to about 200cc/L, about 50cc/L to about 175cc/L, about 50cc/L to about 150cc/L, about 50cc/L to about 125cc/L, about 50cc/L to about 100cc/L, about 50cc/L to about 75cc/L, about 75cc/L to about 225cc/L, about 75cc/L to about 200cc/L, about 75cc/L to about 175cc/L, about 75cc/L to about 150cc/L, about 75cc/L to about 125cc/L, about 75cc/L to about 100cc/L, about 100cc/L to about 225cc/L, about 100cc/L to about 200cc/L, about 100cc/L to about 175cc/L, about 100cc/L to about 150cc/L, about 100cc/L to about 125cc/L, about 125cc/L to about 200cc/L, about 125cc/L to about 175cc/L, about 125cc/L to about 150cc/L, about 150cc/L to about 225cc/L, about 150cc/L to about 200cc/L, about 150cc/L to about 175cc/L, about 175cc/L to about 225cc/L, about 175cc/L to about 200cc/L, or about 200cc/L to about 225cc/L.

In some other embodiments, the adsorbent comprisesA body defining an outer surface and a three-dimensional low flow resistance shape or morphology. The three-dimensional low flow resistance shape or form may be any shape or form with low flow resistance as would be understood by a person skilled in the art. For example, the three-dimensional low flow resistance shape or morphology may be at least one of a substantially cylindrical body, a substantially oval prism, a substantially sphere, a substantially cube, a substantially elliptical prism, a substantially rectangular prism, a lobed prism, a three-dimensional spiral or helix, or a combination thereof. Other useful examples of morphology include shapes known to those skilled in the absorber packing art and include Raschig rings (Raschig rings), crossover spacer rings,

Ring(s)>

Saddle, berl saddle, super +.>

Saddle, conjugated ring, cascade mini ring and lux ring. Other useful examples of forms include shapes known to those of skill in pasta making (pasta making) and may include ribbon, solid, hollow, leaf, and leaf-hollow composite shapes of strips, springs, coils, bottle opener, shells, tubes, such as double-screw pasta (gemelli), screw powder (fuzil), through-core helicoidal (buco), macaroni (macaroni), corrugated shell macaroni (regatoni), screw pasta (cellentani), butterfly (farsurface), gomiti ritti, rolled pasta (casaneci), smooth shell pasta (canvaselli), creste di-gali, spiral short pasta (gigli), bovine pasta (lumaconi), wave surface (quadreffeire), pasta (snail), round pasta (ruote), textured pasta (conglie), or combinations thereof

As non-limiting examples, fig. 1A-1I illustrate exemplary shape configurations of the present disclosure, including a composite leaf shape (a), a square prism shape (B), a cylindrical shape (C), a shape with a star-shaped cross-section (D), a cross-section (E), a triangular prism with an inner wall traversing the central axis (F), a triangular prism with an inner wall not traversing the central axis (G), a spiral or twisted ribbon shape (H1 with an appearance of one end of H2), and a hollow cylinder (I).

The cross-sectional width of the particulate adsorbent material may be about 1mm to about 20mm (e.g., about 1mm, about 2mm, about 3mm, about 4mm, about 5mm, about 6mm, about 7mm, about 8mm, about 9mm, about 10mm, about 11mm, about 12mm, about 13mm, about 14mm, about 15mm, about 16mm about 17mm, about 18mm, about 19mm, or about 20 mm). In particular embodiments, the cross-sectional width is from about 1mm to about 18mm, from about 1mm to about 16mm, from about 1mm to about 14mm, from about 1mm to about 12mm, from about 1mm to about 10mm, from about 1mm to about 8mm, from about 1mm to about 6mm, from about 1mm to about 4mm, from about 1mm to about 3mm, from about 2mm to about 20mm, from about 2mm to about 18mm, from about 2mm to about 16mm, from about 2mm to about 14mm, from about 2mm to about 12mm, from about 2mm to about 10mm, from about 2mm to about 8mm, from about 2mm to about 6mm, from about 2mm to about 4mm, from about 4mm to about 20mm, from about 4mm to about 18mm, from about 4mm to about 16mm, from about 4mm to about 14mm, from about 4mm to about 12mm, from about 4mm to about 10mm, from about 4mm to about 8mm, from about 4mm to about 6mm, about 6mm to about 20mm, about 6mm to about 18mm, about 6mm to about 16mm, about 6mm to about 14mm, about 6mm to about 12mm, about 6mm to about 10mm, about 6mm to about 8mm, about 8mm to about 20mm, about 8mm to about 18mm, about 8mm to about 16mm, about 8mm to about 14mm, about 8mm to about 12mm, about 8mm to about 10mm, about 10mm to about 20mm, about 10mm to about 18mm, about 10mm to about 16mm, about 10mm to about 14mm, about 10mm to about 12mm, about 12mm to about 20mm, about 12mm to about 18mm, about 12mm to about 16mm, about 12mm to about 14mm to about 20mm, about 14mm to about 18mm, about 14mm to about 16mm, about 16mm to about 20mm, about 16mm to about 18mm, or about 18mm to about 20mm.

The adsorbent may include at least one cavity in fluid communication with an outer surface of the adsorbent.

The cross-section of the adsorbent may be hollow in shape.

The sorbent may include at least one channel in fluid communication with the at least one outer surface.

In certain further embodiments, each portion of the adsorbent has a thickness equal to or less than about 3.0mm. For example, the thickness of each portion of the adsorbent may be equal to or less than 2.5mm, equal to or less than 2.0mm, equal to or less than 1.5mm, equal to or less than 1.25mm, equal to or less than 1.0mm, equal to or less than 0.75mm, equal to or less than 0.5mm, or equal to or less than 0.25mm. That is, each portion of the adsorbent may have a thickness of about 0.1mm to about 3mm, about 0.1mm to about 2.5mm, about 0.1mm to about 2.0mm, about 0.1mm to about 1.5mm, about 0.1mm to about 1.0mm, about 0.1mm to about 0.5mm, about 0.2mm to about 3mm, about 0.2mm to about 2.5mm, about 0.2mm to about 2.0mm, about 0.2mm to about 1.5mm, about 0.2mm to about 1.0mm, about 0.2mm to about 0.5mm, about 0.4mm to about 3mm, about 0.4mm to about 1.5mm, about 0.4mm to about 1.0mm, about 0.4mm to about 3mm, about 0.4mm to about 2.5mm, about 2.4 mm to about 2.5mm, about 2.2 mm to about 2.5mm, about 1.5mm to about 2.5mm, about 0.2mm to about 2.5mm, about 0.5mm to about 1.5mm, about 0.5mm to about 2.5mm, about 0.4mm to about 2.5mm, about 1.5mm to about 2.5mm, about 0.5mm to about 2.5 mm.

In one embodiment, the thickness of at least one outer wall of the hollow shape is equal to or less than about 1.0mm (e.g., about 0.1mm, about 0.2mm, about 0.3mm, about 0.4mm, about 0.5mm, about 0.6mm, about 0.7mm, about 0.8mm, about 0.9mm, or about 1.0 mm). For example, the hollow shaped outer wall has a thickness of about 0.1mm to about 1.0mm, about 0.1mm to about 0.9mm, about 0.1mm to about 0.8mm, about 0.1mm to about 0.7mm, about 0.1mm to about 0.6mm, about 0.1mm to about 0.5mm, about 0.1mm to about 0.4mm, about 0.1mm to about 0.3mm, about 0.1mm to about 0.2mm, about 0.2mm to about 1.0mm, about 0.2mm to about 0.9mm, about 0.2mm to about 0.8mm, about 0.2mm to about 0.7mm, about 0.2mm to about 0.6mm, about 0.2mm to about 0.5mm, about 0.2mm to about 0.4mm, about 0.2mm to about 0.3mm, about 0.3mm to about 1.0mm, about 0.3mm to about 0.9mm, about 0.2mm to about 0.8mm, about 0.3mm to about 0.5mm, about 0.3mm to about 0.4mm, about 0.4mm to about 1.0mm, about 0.4mm to about 0.9mm, about 0.4mm to about 0.8mm, about 0.4mm to about 0.7mm, about 0.4mm to about 0.6mm, about 0.4mm to about 0.5mm, about 0.5mm to about 1.0mm, about 0.5mm to about 0.9mm, about 0.5mm to about 0.8mm, about 0.5mm to about 0.7mm, about 0.5mm to about 0.6mm, about 0.6mm to about 1.0mm, about 0.6mm to about 0.9mm, about 0.6mm to about 0.8mm, about 0.6mm to about 0.7mm, about 0.7mm to about 1.0mm, about 0.7mm to about 0.9mm, about 0.7mm to about 0.8mm, about 0.8mm to about 0.9mm, or about 1.9 mm.

In other embodiments, the hollow shape has at least one inner wall extending between outer walls, and the at least one inner wall has a thickness equal to or less than about 1.0mm (e.g., about 0.1mm, about 0.2mm, about 0.3mm, about 0.4mm, about 0.5mm, about 0.6mm, about 0.7mm, about 0.8mm, about 0.9mm, or about 1.0 mm). For example, the thickness of the inner wall may be from about 0.1mm to about 1.0mm, from about 0.1mm to about 0.9mm, from about 0.1mm to about 0.8mm, from about 0.1mm to about 0.7mm, from about 0.1mm to about 0.6mm, from about 0.1mm to about 0.5mm, from about 0.1mm to about 0.4mm, from about 0.1mm to about 0.3mm, from about 0.1mm to about 0.2mm, from about 0.2mm to about 1.0mm, from about 0.2mm to about 0.9mm, from about 0.2mm to about 0.8mm, from about 0.2mm to about 0.7mm, from about 0.2mm to about 0.6mm, from about 0.2mm to about 0.5mm, from about 0.2mm to about 0.4mm, from about 0.2mm to about 0.3mm, from about 0.3mm to about 1.0mm, from about 0.3mm to about 0.3mm, from about 0.2mm to about 0.9mm, from about 0.3mm to about 0.3mm, about 0.3mm to about 0.5mm, about 0.3mm to about 0.4mm, about 0.4mm to about 1.0mm, about 0.4mm to about 0.9mm, about 0.4mm to about 0.8mm, about 0.4mm to about 0.7mm, about 0.4mm to about 0.6mm, about 0.4mm to about 0.5mm, about 0.5mm to about 1.0mm, about 0.5mm to about 0.9mm, about 0.5mm to about 0.8mm, about 0.5mm to about 0.7mm, about 0.5mm to about 0.6mm, about 0.6mm to about 1.0mm, about 0.6mm to about 0.9mm, about 0.6mm to about 0.8mm, about 0.6mm to about 0.7mm, about 0.7mm to about 1.0mm, about 0.7mm to about 0.9mm, about 0.7mm to about 0.8mm, about 0.8mm to about 0.8mm, or about 0.8 mm.

In particular embodiments, the thickness of at least one of the inner wall, the outer wall, or a combination thereof is equal to or less than about 1.0mm (e.g., about 0.1mm, about 0.2mm, about 0.3mm, about 0.4mm, about 0.5mm, about 0.6mm, about 0.7mm, about 0.8mm, about 0.9mm, or about 1.0 mm). For example, the thickness of at least one of the inner wall, the outer wall, or a combination thereof is equal to or less than about 1.0mm, equal to or less than about 0.6mm, or equal to or less than about 0.4mm. In certain embodiments, at least one of the inner wall, the outer wall, or a combination thereof has a thickness of about 0.1mm to about 1.0mm, about 0.1mm to about 0.9mm, about 0.1mm to about 0.8mm, about 0.1mm to about 0.7mm, about 0.1mm to about 0.5mm, about 0.1mm to about 0.4mm, about 0.1mm to about 0.3mm, about 0.1mm to about 0.2mm, about 0.2mm to about 0.1mm, about 0.7mm to about 0.9mm, about 0.2mm to about 0.6mm, about 0.2mm to about 0.5mm, about 0.2mm to about 0.4mm, about 0.2mm to about 0.3mm, about 0.3mm to about 0.3mm, about 0.1mm to about 0.4mm to about 0.6mm, about 0.1mm to about 0.8mm, about 0.3mm to about 0.8mm, about 0.7mm to about 0.8mm to about 0.7mm, about 0.9mm to about 0.7mm, about 0.8mm to about 0.7 mm.

In some embodiments, the inner wall extends outwardly from the hollow of the particulate adsorbent material (e.g., from the center of the particulate adsorbent material) to the outer wall in at least two directions.

For example, the inner wall may extend outwardly from the hollow of the particulate adsorbent material (e.g., from the center of the particulate adsorbent material) in at least three directions or from the hollow of the particulate adsorbent material (e.g., from the center of the particulate adsorbent material) in at least four directions to the outer wall.

In certain embodiments, the particulate adsorbent material may have a length of about 1mm to about 20mm (e.g., about 1mm, about 2mm, about 3mm, about 4mm, about 5mm, about 6mm, about 7mm, about 8mm, about 9mm, about 10mm, about 11mm, about 12mm, about 13mm, about 14mm, about 15mm, about 16mm about 17mm, about 18mm, about 19mm, or about 20 mm). In particular embodiments, the length is from about 1mm to about 18mm, from about 1mm to about 16mm, from about 1mm to about 14mm, from about 1mm to about 12mm, from about 1mm to about 10mm, from about 1mm to about 8mm, from about 1mm to about 6mm, from about 1mm to about 4mm, from about 1mm to about 3mm, from about 2mm to about 20mm, from about 2mm to about 18mm, from about 2mm to about 16mm, from about 2mm to about 14mm, from about 2mm to about 12mm, from about 2mm to about 10mm, from about 2mm to about 8mm, from about 2mm to about 6mm, from about 2mm to about 4mm, from about 4mm to about 20mm, from about 4mm to about 18mm, from about 4mm to about 16mm, from about 4mm to about 14mm, from about 4mm to about 12mm, from about 4mm to about 10mm, from about 4mm to about 8mm, from about 4mm to about 6mm, from about 6mm to about 20mm, about 6mm to about 18mm, about 6mm to about 16mm, about 6mm to about 14mm, about 6mm to about 12mm, about 6mm to about 10mm, about 6mm to about 8mm, about 8mm to about 20mm, about 8mm to about 18mm, about 8mm to about 16mm, about 8mm to about 14mm, about 8mm to about 12mm, about 8mm to about 10mm, about 10mm to about 20mm, about 10mm to about 18mm, about 10mm to about 16mm, about 10mm to about 14mm, about 10mm to about 12mm, about 12mm to about 20mm, about 12mm to about 18mm, about 12mm to about 16mm, about 12mm to about 14mm, about 14 to about 20mm, about 14mm to about 18mm, about 14mm to about 16mm, about 16mm to about 20mm, about 16mm to about 18mm, or about 18mm to about 20mm.

The particulate adsorbent may further comprise at least one of the following: a pore-forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of 100 ℃ or more; an adhesive; a filler; or a combination thereof.

In a particular embodiment, the particulate adsorbent comprises at least one of the following: about 5% to about 60% of an adsorbent, about 60% or less of a filler, about 6% or less of a pore forming material (or processing aid), about 10% or less of a silicate, about 5% to about 70% of a clay, or a combination thereof. The adsorbent may be present at about 5% to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%, about 20% to about 60%, about 20% to about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about 60%, about 30% to about 50%, about 30% to about 40%, about 40% to about 60%, about 40% to about 50%, or about 50% to about 60% of the particulate adsorbent material.

The filler may be present in less than or equal to about 60%, less than or equal to about 50%, less than or equal to about 40%, less than or equal to about 30%, less than or equal to about 20%, less than or equal to about 10%, from about 5% to about 60%, from about 5% to about 50%, from about 5% to about 40%, from about 5% to about 30%, from about 5% to about 20%, from about 5% to about 10%, from about 10% to about 60%, from about 10% to about 50%, from about 10% to about 40%, from about 10% to about 30%, from about 10% to about 20%, from about 20% to about 60%, from about 20% to about 50%, from about 20% to about 40%, from about 20% to about 30%, from about 30% to about 50%, from about 30% to about 40%, from about 40% to about 60%, from about 40% to about 50%, or from about 50% to about 60% of the particulate adsorbent material.

The pore forming material may be present at less than or equal to about 6%, less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, less than or equal to about 2%, or less than or equal to about 1% of the particulate adsorbent material.

The silicate may be present in less than or equal to about 10%, less than or equal to about 9%, less than or equal to about 8%, less than or equal to about 7%, less than or equal to about 6%, less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, less than or equal to about 2%, or less than or equal to about 1% of the particulate adsorbent material.

The clay may be present from about 5% to about 70%, from about 5% to about 60%, from about 5% to about 50%, from about 5% to about 40%, from about 5% to about 30%, from about 5% to about 20%, from about 5% to about 10%, from about 10% to about 70%, from about 10% to about 60%, from about 10% to about 50%, from about 10% to about 40%, from about 10% to about 30%, from about 10% to about 20%, from about 20% to about 70%, from about 20% to about 60%, from about 20% to about 50%, from about 20% to about 40%, from about 20% to about 30%, from about 30% to about 70%, from about 30% to about 60%, from about 30% to about 50%, from about 30% to about 40%, from about 40% to about 70%, from about 40% to about 60%, from about 40% to about 50%, from about 50% to about 70%, from about 50% to about 60%, or from about 60% to about 70%.

The porogen (or processing aid) creates macroscopic pores upon sublimation, evaporation, chemical decomposition, dissolution, or melting. This provides for spatial dilution of the adsorbent material. The pore-forming material may be a cellulose derivative, such as methylcellulose, carboxymethylcellulose, polyethylene glycol, phenol-formaldehyde resins (novolacs, resoles), polyethylene or polyester resins. Cellulose derivatives may include copolymers having methyl groups and/or having hydroxypropyl and/or hydroxyethyl moiety substitution. The porogen or processing aid may sublimate, evaporate, chemically decompose, dissolve or melt when heated to a temperature in the range of about 125 ℃ to about 640 ℃. For example, the number of the cells to be processed, when heated to about 125 to about 600 ℃, about 125 to about 550 ℃, about 125 to about 500 ℃, about 125 to about 450 ℃, about 125 to about 400 ℃, about 125 to about 350 ℃, about 125 to about 300 ℃, about 125 to about 250 ℃, about 125 to about 200 ℃, about 200 to about 350 ℃, about 200 to about 300 ℃, about 150 to about 250 ℃, about 150 to about 600 ℃, about 150 to about 550 ℃, about 150 to about 500 ℃, about 150 to about 450 ℃, about 150 to about 400 ℃, about 150 to about 350 ℃, about 150 to about 300 ℃, about 150 to about 250 ℃, about 150 to about 200 ℃, about 200 to about 640 ℃, about 200 to about 600 ℃, about 200 to about 550 ℃, about 200 to about 500 ℃, about 200 to about 450 ℃, about 200 to about 400 ℃, about 200 to about 350 ℃, about 200 to about 300 ℃, about 200 to about 250 ℃, about 250 to about 640 ℃, about 250 to about 600 ℃, about 250 to about 550 ℃, about 250 to about 500 ℃, about 250 to about 600 ℃, about 200 to about 500 ℃. About 250 to about 450, about 250 to about 400, about 250 to about 350, about 300 to about 640, about 300 to about 600, about 300 to about 550, about 300 to about 500, about 300 to about 450, about 300 to about 400, about 300 to about 350, about 350 to about 640, 350 to about 600, about 350 to about 550, about 350 to about 500, about 350 to about 450, about 350 to about 400, about 400 to about 640, about 400 to about 600, about 400 to about 550, about 400 to about 500, about 400 to about 450, about 450 to about 640, about 450 to about 600, about 450 to about 550, about 450 to about 500, about 500 to about 640, about 500 to about 500, about 500 to about 600, about 500 to about 550, about 550 to about 640, about 550 to about 600, or about 600 to about 640, the processing aid may sublimate, evaporate, chemically decompose, dissolve or melt.

The binder may be a clay or silicate material. For example, the binder may be at least one of zeolite clay, bentonite, montmorillonite clay, illite clay, french green mud, paspalite clay, redmond clay, terramin clay, activated clay, fuller's earth clay, orialite clay, vitalilite clay, rectorite clay, cordierite, or combinations thereof.

Fillers can be used in the particulate adsorbent structure to aid and maintain shape formation and mechanical integrity, as well as to increase the amount of macropore volume in the final particulate product. In one embodiment, the filler is a solid or hollow microsphere, which may be micron-sized or larger. In other embodiments, the filler is an inorganic filler, such as a glass material and/or a ceramic material. The filler may be any suitable filler that will be appreciated by those skilled in the art to provide the benefits described above.

In another aspect, the present disclosure provides a method of preparing a particulate adsorbent material. The method comprises the following steps: mixing an adsorbent having microscopic pores with a diameter of less than about 100nm with a pore-forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of 100 ℃ or more; the mixture is heated to a temperature of about 100 ℃ to about 1200 ℃ for about 0.25 hours to about 24 hours, forming macroscopic pores having a diameter of about 100nm or greater when the nuclear material sublimates, evaporates, chemically decomposes, dissolves, or melts, wherein the ratio of the volume of macroscopic pores to the volume of microscopic pores in the adsorbent is greater than 150%. The adsorbent may have any of the features of the particulate adsorbent materials discussed in this disclosure.

The mixture may be heated to about 100 to about 1100 ℃, about 100 to about 1000 ℃, about 100 to about 900 ℃, about 100 to about 800 ℃, about 100 to about 700 ℃, about 100 to about 600 ℃, about 100 to about 500 ℃, about 100 to about 400 ℃, about 100 to about 300 ℃, about 100 to about 200 to about 1200 ℃, about 200 to about 1100 ℃, about 200 to about 1000 ℃, about 200 to about 900 ℃, about 200 to about 800 ℃, about 200 to about 700 ℃, about 200 to about 600 ℃, about 200 to about 500 ℃, about 200 to about 400 ℃, about 200 to about 300 ℃, about 300 to about 1200 ℃, about 300 to about 1100 ℃, about 300 to about 1000 ℃, about 300 to about 900 ℃, about 300 to about 700 ℃, about 300 to about 600 ℃, about 300 to about 500 ℃, about 400 to about 1200 ℃, about 400 to about 1100 ℃, about 400 to about 1000, about 400 to about 800, about 400 to about 700, about 400 to about 600, about 400 to about 500, about 500 to about 1200, about 500 to about 1100, about 500 to about 1000, about 500 to about 900, about 500 to about 800, about 500 to about 700, about 500 to about 600, about 600 to about 1200, about 600 to about 1000, about 600 to about 800, about 700 to about 1200, about 700 to about 1100, about 700 to about 1000, about 700 to about 900, about 800 to about 800, about 800 to about 1100, about 800 to about 1000, about 800 to about 900, about 900 to about 1200, about 900 to about 1100, about 900 to about 1000, about 1000 ℃ to about 1100 ℃, or about 1100 ℃ to about 1200 ℃.

In some embodiments, heating the mixture may include a ramp rate of about 2.5 ℃/minute (e.g., about 1.0 ℃/minute, about 1.25 ℃/minute, about 1.5 ℃/minute, about 1.75 ℃/minute, about 2.0 ℃/minute, about 2.25 ℃/minute, about 2.75 ℃/minute, about 3.0 ℃/minute, about 3.25 ℃/minute, about 3.5 ℃/minute, about 3.75 ℃/minute, about 4.0 ℃/minute, or 4.25 ℃/minute). For example, the heating rate may be about 0.5 to about 20, about 0.5 to about 15, about 0.5 to about 10, about 0.5 to about 5.0, about 0.5 to about 2.5, about 1.0 to about 20, about 1.0 to about 15, about 1.0 to about 10, about 1.0 to about 5.0, about 1.0 to about 2.5, about 2.0 to about 20, about 2.0 to about 15, about 2.0 to about 10, about 2.0 to about 5.0, about 2.0 to about 2.5, about 5.0 to about 5.0, about 2.0 to about 5, about 10 to about 10, about 5.0 to about 20, about 5.0 to about 15, about 10 to about 10, about 10 to about 20, or about 15. For example, the temperature rise may be performed for about 5 minutes to about 2 hours, about 5 minutes to about 1.75 hours, about 5 minutes to about 1.5 hours, about 5 minutes to about 1.25 hours, about 5 minutes to about 1.0 hour, about 5 minutes to about 45 minutes, about 5 minutes to about 30 minutes, about 5 minutes to about 15 minutes, about 15 minutes to about 2 hours, about 15 minutes to about 1.75 hours, about 15 minutes to about 1.5 hours, about 15 minutes to about 1.25 hours, about 15 minutes to about 1.0 hours, about 15 minutes to about 45 minutes, about 15 minutes to about 30 minutes, about 30 minutes to about 2 hours, about 30 minutes to about 1.75 hours, about 30 minutes to about 1.5 hours, about 30 minutes to about 45 minutes, about 45 minutes to about 2 hours, about 45 minutes to about 1.75 hours, about 45 minutes to about 1.25 hours, about 15 minutes to about 45 minutes, about 1.25 hours, about 30 minutes to about 1.75 hours, about 30 minutes to about 1.5 hours, about 1.25 hours.

In another embodiment, the mixture is maintained at this temperature (i.e., after warming) for about 0.25 hours to about 24 hours. For example, the mixture may be maintained at that temperature for about 0.25 to about 18 hours, about 0.25 to about 16 hours, about 0.25 to about 14 hours, about 0.25 to about 12 hours, about 0.25 to about 10 hours, about 0.25 to about 8 hours, about 0.25 to about 6 hours, about 0.25 to about 4 hours, about 0.25 to about 2 hours, about 1 to about 24 hours, about 0.25 to about 18 hours, about 1 to about 16 hours, about 1 to about 14 hours, about 1 to about 12 hours, about 1 to about 10 hours, about 1 to about 8 hours, about 1 to about 6 hours, about 1 to about 4 hours, about 1 to about 2 hours, about 2 to about 24 hours, about 2 to about 18 hours, about 2 to about 16 hours, about 1 to about 14 hours, from about 2 hours to about 10 hours, from about 2 hours to about 8 hours, from about 2 hours to about 6 hours, from about 2 hours to about 3 hours, from about 3 hours to about 24 hours, from about 3 hours to about 18 hours, from about 3 hours to about 16 hours, from about 3 hours to about 14 hours, from about 3 hours to about 12 hours, from about 3 hours to about 10 hours, from about 3 hours to about 8 hours, from about 3 hours to about 6 hours, from about 3 hours to about 4 hours, from about 4 hours to about 24 hours, from about 4 hours to about 18 hours, from about 4 hours to about 16 hours, from about 4 hours to about 14 hours, from about 4 hours to about 12 hours, from about 4 hours to about 10 hours, from about 4 hours to about 8 hours, from about 4 hours to about 6 hours, from about 6 hours to about 24 hours, from about 6 hours to about 18 hours, from about 6 hours to about 16 hours, from about 16 hours to about 14 hours, from about 6 hours to about 10 hours, from about 6 hours to about 8 hours, from about 8 hours to about 24 hours, from about 8 hours to about 18 hours, from about 8 hours to about 16 hours, from about 8 hours to about 14 hours, from about 8 hours to about 12 hours, from about 8 hours to about 10 hours, from about 10 hours to about 24 hours, from about 10 hours to about 18 hours, from about 10 hours to about 16 hours, from about 10 hours to about 14 hours, from about 10 hours to about 12 hours, from about 12 hours to about 24 hours, from about 12 hours to about 18 hours, from about 12 hours to about 16 hours, from about 12 hours to about 14 hours, from about 14 hours to about 24 hours, from about 14 hours to about 18 hours, from about 14 hours to about 16 hours, from about 16 hours to about 24 hours, from about 16 hours to about 18 hours, from about 18 hours to about 24 hours, from about 18 hours, from about 22 hours to about 22 hours, from about 22 hours to about 20 hours, or from about 20 hours.

The method may further comprise cooling the mixture (e.g., to room temperature). In one embodiment, the mixture may be cooled for more than about 4 to about 10 hours. For example, the mixture may be cooled for more than about 4 hours to about 9 hours, about 4 hours to about 8 hours, about 4 hours to about 7 hours, about 4 hours to about 6 hours, about 4 hours to about 5 hours, about 5 hours to about 10 hours, about 5 hours to about 9 hours, about 5 hours to about 8 hours, about 5 hours to about 7 hours, about 5 hours to about 6 hours, about 6 hours to about 10 hours, about 6 hours to about 9 hours, about 6 hours to about 8 hours, about 6 hours to about 7 hours, about 7 hours to about 10 hours, about 7 hours to about 9 hours, about 7 hours to about 8 hours, about 8 hours to about 10 hours, about 8 hours to about 9 hours, or about 9 hours to about 10 hours.

In further embodiments, the heating of the mixture is performed in an inert atmosphere (e.g., nitrogen, argon, neon, krypton, xenon, radon, flue gas in which the vapor and oxygen content is controlled, or a combination thereof).

The particulate adsorbent material may have a retention of about 1.0g/dL or less, about 0.75g/dL or less, about 0.50g/dL or less, or about 0.25g/dL or less. For example, the adsorbent may have a retention of about 0.25g/dL to about 1.00g/dL, about 0.25g/dL to about 0.75g/dL, about 0.25g/dL to about 0.50g/dL, about 0.50g/dL to about 1.00g/dL, about 0.50g/dL to about 0.75g/dL, or about 0.75g/dL to about 1.00 g/dL.

In any aspect or embodiment described herein, at least one of the diameters of the microscopic holes is about 2nm to less than about 100nm, the macroscopic holes have a diameter equal to or greater than 100nm and less than 100,000nm, or a combination thereof.

The method may further comprise extruding or compressing the mixture into a shaped structure. For example, the extruded or compressed particulate adsorbent material may include a body defining an outer surface and a three-dimensional low flow resistance shape or morphology. The low flow resistance shape or morphology may be any shape or morphology for the adsorbent material described herein, for example. For example, the three-dimensional low flow resistance shape or morphology may be at least one of a substantially cylindrical body, a substantially oval prism, a substantially sphere, a substantially cube, a substantially elliptical prism, a substantially rectangular prism, a leaf prism, a three-dimensional spiral, the shape or morphology described in fig. 1A-1I, or a combination thereof.

The adsorbent may be at least one of activated carbon, molecular sieves, porous alumina, clay, porous silica, zeolite, metal organic framework, or combinations thereof.

The mixture may comprise a binder (such as clay, silicate, or a combination thereof) and/or a filler. The filler may be any filler known or known in the relevant art.

The adsorbent may have a cross-sectional width as herein, for example in the range of about 1mm to about 20 mm.

The particulate adsorbent material may include at least one cavity or channel in fluid communication with the outer surface of the adsorbent. The cross section of the particulate adsorbent may be hollow in shape. Each portion of the adsorbent may have a thickness of about 3.0mm or less. The thickness of the outer wall of the hollow shape may be 3mm or less (e.g., about 0.1mm to about 1.0 mm). The hollow shape may have an inner wall extending between outer walls, which may have a thickness of, for example, about 3.0mm or less (e.g., about 0.1mm to about 1.0 mm).

The inner wall may extend outwardly from the inner volume (such as from the hollow), such as the center, in at least two directions, at least three directions, or at least four directions to the outer wall.

In some embodiments, the adsorbent has a length of about 1mm to about 20mm, e.g., about 2mm to about 7 mm).

Examples

Test method

Standard method ASTM D2854-09 (2014) (hereinafter "standard method") can be used to determine the apparent density of a particulate adsorbent, taking into account the prescribed minimum ratio 10 of measured cylinder diameter to average particle diameter of particulate material, the average particle diameter being measured according to the prescribed standard screening method.

Standard method ASTM D5228-16 can be used to determine Butane Working Capacity (BWC) for the volume of adsorbent containing particulate particles and/or granulated adsorbent. The retention (g/dL) is calculated as the difference between the volumetric butane activity (g/dL) [ i.e., saturated butane activity on a weight basis (g/100 g) times the apparent density (g/cc) ] and BWC (g/dL).

Macropore volume was measured by mercury intrusion porosimetry ISO 15901-1:2016. The apparatus used in the examples was Micromeritics Autopore V (Norcross, GA). The amount of sample used was about 0.4g and was pretreated in an oven at 105℃for at least 1 hour. The surface tension and contact angle of mercury used in the Washburn equation are 485 dyne/cm (dyne/cm) and 130 deg., respectively.

Microscopic pore volumes were measured by nitrogen adsorption porosimetry by nitrogen adsorption method ISO 15901-2:2006 using Micromeritics ASAP 2420 (Norcross, GA). The sample preparation procedure was deaeration to less than 10 mu mmHg. The pore volume was determined for the microscopic pore size, which is the desorption branch from the 77K isotherm of the 0.1g sample. The nitrogen adsorption isotherm data was analyzed by Kelvin and Halsey equations to determine the pore volume distribution with cylindrical pore diameter according to model Barrett, joyner and Halenda ("BJH"). The non-ideality factor is 0.0000620. The density conversion factor was 0.0015468. The diameter of the hard heat transpiration ball is

The molecular cross-sectional area is 0.162nm ² . For calculation and pore diameter (D, +.>

) Related coacervate thickness->

0.4977[ ln (D)] ² 0.6981ln (D) +2.5074. The target relative pressures for the isotherms are as follows: 0.04, 0.05, 0.085, 0.125, 0.15, 0.18, 0.2, 0.355, 0.5, 0.63, 0.77, 0.9, 0.95, 0.995, 0.95, 0.9, 0.8, 0.7, 0.6, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.12, 0.1, 0.07, 0.05, 0.03, 0.01. The actual values are recorded within an absolute or relative pressure tolerance of 5mmHg or 5%, respectively, whichever is more stringent. The time between successive pressure readings during equilibration is 10 seconds.

For different shapes of adsorbent particles, the pressure drop (Pa/cm) was measured as a flow restriction at a given Standard Liter Per Minute (SLPM) over a dense packed bed of 30mm length using the apparatus shown in FIG. 4. Specifically, at the center of the particle bed of diameter 43mm, the pressure drop (Pa/cm) across a depth of 30mm was measured, with an air flow rate in the range of 10-70SLPM (24-165 cm/s). The adsorbent was packed into a tube of internal diameter 43mm with port holes drilled at +/-15mm measured from the midpoint along the depth of the bed. Open cell foam is used to contain the carbon bed. For pressure purging, compressed air is loaded through port 1 into the atmosphere on port 2; the pressure drop across

ports

3 and 4 is measured. For vacuum purging, vacuum is drawn through port 1; the pressure drop was measured over

ports

3 and 4. Flow was regulated from 10-70SLPM (24-165 cm/s) and pressure drop was measured at each regulation.

The strength of the sorbent particles of the present disclosure was examined using a variation of the standard ASTM 3802-79 method that is acceptable in the art. U.S. patent No. 6,573,212 details the process as a wear hardness test and reports the results as particle strength. As indicated in us patent 5,324,703, the typical minimum acceptable strength for this industry standard test is 55.

Preparing the particle adsorption material.As described below, by mixing

Exemplary particulate adsorbent materials were prepared from activated carbon powder, kaolin clay, nepheline syenite (mineral component added to the clay), calcined kaolin (clay), methylcellulose, sodium silicate, and hollow borosilicate glass microspheres. The general compositions of the exemplary particulate adsorbent materials (E-1 to E-6) and comparative examples (C-1 to C-14) are shown in tables 1 and 2, and C-14 is a commercially available product. In particular, the sorbents are obtained from commercially available Honda Civic emission control tanks. Those skilled in the art will appreciate that many variations in the formulation will result in the production of the particulate adsorbent material of the present disclosure.

Table 1. General composition of exemplary particulate adsorbent materials.

TABLE 2 compositions of example E-3

The components of the particulate adsorbent material are mixed in the mixer in the amounts described above. The dry ingredients are added to the apparatus, followed by silicate and sufficient water to obtain an extrudable paste. A variety of types of mixers can be used to achieve uniform distribution of ingredients and high shear mixing is required to produce a paste with proper extrusion rheology. Those skilled in the art will appreciate that many types of extruders are effective for the mixtures of the present disclosure to produce the particulate adsorbent materials of the present disclosure.

The extrusion die consists of a porous plate with inserts that direct the material flow through to create hollow pellets. Most examples use a cylindrical tube with a shaped support in the middle, as shown in fig. 1C, but any of a variety of low flow restriction shapes are contemplated by the present disclosure. The extrudate had an outer diameter of 5.0mm and the wall thickness of the outer wall and support was 0.75mm. The hollow composite leaf shape (see fig. 1A), hollow rectangular prism shape (see fig. 1B) and hollow triangular prism shape (see fig. 1G) have similar nominal outer dimensions (i.e., about 4-7mm outer diameter and about 0.5-1.0mm thick wall), exhibiting similar test results (data not shown). Due to the nominal outer diameter (i.e., cross-sectional width), fig. 1A-1I show the embodiment as "d": the side widths of the square cross-sections (fig. 1B) are the widths shown for the composite leaf (fig. 1A), star (fig. 1D), cross or 'X' shaped (fig. 1E) and triangle (fig. 1F and 1G) cross-sections and for the twist tapes in a spiral (fig. 1H1 having the width shown in fig. 1H 2).

The extrudate was cut to a target length of about 5mm or about 10mm with a rotary cutter and then dried overnight on a tray placed in a convection oven at about 110 ℃. However, the pellets may be dried on a forced air belt dryer, in a rotary kiln, or by using any oven with sufficient air flow and low humidity.

The dried granules/pellets are then calcined in a box furnace, tube furnace or rotary kiln under an inert nitrogen atmosphere. Most samples were prepared as follows: the temperature is raised to about 1100 c at a rate of about 2.5 c/min, held at the highest temperature for about 3 hours, and then cooled to room temperature over about 6-8 hours. Various calcination conditions appear to be suitable. The temperature rise time was studied as fast as about 10 minutes with a hold time as short as 20 minutes. Temperatures exceeding 900 c appear to ensure good pellet strength, but are not required. Any inert atmosphere (e.g., nitrogen, argon, or may be flue gas) may be utilized as long as the steam and oxidation levels are controlled. The inventors have successfully prepared good products in a rotary kiln with a nitrogen atmosphere at about 970 c with a residence time of 30 minutes.

Retention test of adsorbent particles. By varying the proportions of the ingredients, exemplary particulate adsorbent materials having a range of pore ratio properties are prepared with a ratio of macroscopic pore volumes of about 100nm or greater to microscopic pore volumes of less than 100nm of from about 47% to about 1333%. The data are given in fig. 2 and table 3. Surprisingly and unexpectedly, it was observed that adsorbent particles having a ratio greater than 150% had significantly lower retention relative to a comparative example having a ratio of less than 150%, such as the commercially available comparative example C-14 (e.g., example E-5 having a 190% ratio of 0.48g/dL and example E-3 having a 241% ratio of 0.34 g/dL). The benefit of this retention is in sharp contrast to the trend taught by U.S. patent 9,174,195, where retention between 65% and 150% asymptotes to above 1g/dL, and examples of ratios above 150% are above the mentioned 1.7g/dL target.

Inspection of adsorbent particle strength. The data are shown in table 3 and fig. 3. Surprisingly, it was found that adsorbent particles having a ratio of macroscopic pore volume of about 100nm or more to microscopic pore volume of less than 100nm of greater than 150% have significant particle strength, independent of the pore ratio, as shown in fig. 3. In contrast, U.S. Pat. No. 9,174,195 shows that when the above ratio is 150% or more, the adsorbent material strength drastically decreases (see, for example, C-14).

TABLE 3 Properties of sorbent compositions

Inspection of pressure drop of adsorbent particles. Tables 4 and 5 show the flow restriction performance of the alternative shape adsorbent material in terms of pressure drop between two points within the packed bed of particulate material. It is apparent to the inventors that the performance is strongly driven by the nominal outer diameter dimension as the primary effect, compared to the "hollow" shape. Accordingly, those skilled in the art will appreciate the nominal outer diameter effect of the selected shape to adjust the flow restriction characteristics (convection requirements). The person skilled in the art will then adjust the hollow cell size, cell volume and wall thickness to adjust the required amount of wall material to balance the working capacity and strength with the adsorption and desorption properties of the adsorbate. For spirals or spirals without defined cells, the belt width and twist pitch are adjusted to obtain flow restrictions, the belt thickness is adjusted to obtain strength and adsorption and desorption properties, and the pitch and thickness are adjusted to obtain working capacity.

TABLE 4 pressure drop data for adsorbent particles

Detailed Description

In one aspect, the present disclosure provides a particulate adsorbent material that can be used for evaporative emission control. The material comprises: an adsorbent having microscopic pores with a diameter of less than about 100 nm; macroscopic pores having a diameter of about 100nm or greater; and the ratio of the volume of macropores to the volume of micropores is greater than about 150%, wherein the retention of the particulate adsorbent material is about 1.0g/dL or less.

In any aspect or embodiment herein, the retention of the particulate adsorbent material is about 0.75g/dL or less.

In any aspect or embodiment herein, the retention of the particulate adsorbent material is from about 0.25 to about 1.00g/dL.

In any aspect or embodiment herein, the particulate adsorbent material is at least one of activated carbon, carbon charcoal, molecular sieves, porous polymers, porous alumina, clay, porous silica, kaolin, zeolite, metal organic framework, titania, ceria, or combinations thereof.

In any aspect or embodiment herein, the micropore volume (as determined by, for example, BJH) of the particulate adsorbent material is about 0.5cc/g or less (about 225cc/L or less).

In any aspect or embodiment herein, the particulate adsorbent material includes a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

In any aspect or embodiment herein, the three-dimensional low flow resistance shape or morphology is at least one of a substantially cylindrical body, a substantially oval prism, a substantially spherical body, a substantially cubic body, a substantially elliptical prism, a substantially rectangular prism, a trilobal prism, a three-dimensional spiral, or a combination thereof.

In any aspect or embodiment herein, the particulate adsorbent material has a cross-sectional width of from about 1mm to about 20mm.

In any aspect or embodiment herein, the cross-sectional width is from about 3mm to about 7mm.

In any aspect or embodiment herein, the particle adsorbing material has a hollow cross-section.

In any aspect or embodiment herein, the particulate adsorbent material comprises at least one cavity in fluid communication with an outer surface of the adsorbent.

In any aspect or embodiment herein, each portion of the particulate adsorbent material has a thickness of about 0.1mm to about 3.0mm.

In any aspect or embodiment herein, the thickness of the at least one outer wall of the hollow shape is in the range of about 0.1mm to about 1.0 mm.

In any aspect or embodiment herein, the hollow shape has at least one inner wall extending between the outer walls and having a thickness of about 0.1mm to about 1.0 mm.

In any aspect or embodiment herein, the thickness of at least one of the inner wall, the outer wall, or a combination thereof is from about 0.3mm to about 0.8mm.

In any aspect or embodiment herein, the thickness of at least one of the inner wall, the outer wall, or a combination thereof is from about 0.4mm to about 0.7mm.

In any aspect or embodiment herein, the inner wall extends outwardly from the hollow of the particulate adsorbent material (such as from the center of the particulate adsorbent material) to the outer wall in at least two directions.

In any aspect or embodiment herein, the inner wall extends outwardly from the hollow of the particulate adsorbent material (such as from the center of the particulate adsorbent material) to the outer wall in at least three directions.

In any aspect or embodiment herein, the inner wall extends outwardly from the hollow of the particulate adsorbent material (such as from the center of the particulate adsorbent material) to the outer wall in at least four directions.

In any aspect or embodiment herein, the particulate adsorbent material has a length of from about 1mm to about 20mm.

In any aspect or embodiment herein, the length is from about 2mm to about 15mm.

In any aspect or embodiment herein, the length is from about 3mm to about 8mm.

In any aspect or embodiment herein, the activated carbon is derived from at least one member selected from the group consisting of wood, wood chips, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit pits, nut shells, nut pits, sawdust, palm, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof.

In any aspect or embodiment herein, the clay is at least one of a zeolite clay, bentonite clay, montmorillonite clay, illite clay, french green clay, pasolite clay, redmond clay, terramin clay, activated clay, fuller's earth clay, orialite clay, vitalite clay, rectorite clay, or a combination thereof.

In any aspect or embodiment herein, the particulate adsorbent material further comprises at least one of the following: a pore-forming material or processing aid that decomposes, dissolves, sublimates, evaporates or melts when heated to a temperature of 100 ℃ or more; an adhesive; a filler; or a combination thereof.

In any aspect or embodiment herein, the pore forming material or processing aid is a cellulose derivative.

In any aspect or embodiment herein, the pore forming material or processing aid is methylcellulose.

In any aspect or embodiment herein, the porogen or processing aid sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of about 125 ℃ to about 640 ℃.

In any aspect or embodiment herein, the binder is a clay or silicate material.

In any aspect or embodiment herein, the packed bed of particulate adsorbent material has a pressure drop <40Pa/cm at an apparent linear air flow rate of 46 cm/s.

In a further aspect, the present disclosure provides a method of making the particulate adsorbent of the present disclosure. The method comprises the following steps: mixing an adsorbent having microscopic pores with a diameter of less than about 100nm with a pore-forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of 100 ℃ or more; and heating the mixture to a temperature of about 100 ℃ to about 1200 ℃ for about 0.25 hours to about 24 hours, forming macroscopic pores having a diameter of about 100nm or greater when the nuclear material sublimates, evaporates, chemically decomposes, dissolves, or melts, wherein the particulate adsorbent has a ratio of macroscopic pore volume to microscopic pore volume of greater than 150%.

In any aspect or embodiment herein, the method further comprises extruding or compressing the mixture into a shaped structure.

In any aspect or embodiment herein, the adsorbent is at least one of activated carbon, molecular sieve, porous alumina, clay, porous silica, zeolite, metal-organic framework, or a combination thereof.

In any aspect or embodiment herein, the mixture further comprises a binder.

In any aspect or embodiment herein, the binder is at least one of clay, silicate, or a combination thereof.

In any aspect or embodiment herein, the mixture further comprises a filler.

In any aspect or embodiment herein, the cross-sectional width of the particulate adsorbent is from about 1mm to about 20mm.

In any aspect or embodiment herein, the particulate adsorbent comprises a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

In any aspect or embodiment herein, the three-dimensional low flow resistance shape or morphology is at least one of a substantially cylindrical, substantially oval prism, substantially spherical, substantially cubic, substantially elliptical prism, substantially rectangular prism, lobed prism, three-dimensional spiral or helix, or a combination thereof.

In any aspect or embodiment herein, the particulate adsorbent comprises at least one cavity or channel in fluid communication with an outer surface of the particulate adsorbent.

In any aspect or embodiment herein, the cross-section of the particulate adsorbent is hollow in shape.

In any aspect or embodiment herein, each portion of the particulate adsorbent has a thickness of about 0.1mm to about 3.0mm.

In any aspect or embodiment herein, the thickness of the outer wall of the hollow shape is from about 0.1mm to about 1.0mm.

In any aspect or embodiment herein, the hollow shape has at least one inner wall extending between outer walls.

In any aspect or embodiment herein, the thickness of the inner wall is from about 0.1mm to about 1.0mm.

In any aspect or embodiment herein, the at least one inner wall, the at least one outer wall, or a combination thereof is from about 0.1mm to about 0.8mm.

In any aspect or embodiment herein, the inner wall extends outwardly from the inner volume, such as the center, to the outer wall in at least two directions.

In any aspect or embodiment herein, the inner wall extends outwardly from the inner volume, such as the center, to the outer wall in at least three directions.

In any aspect or embodiment herein, the inner wall extends outwardly from the inner volume, such as the center, to the outer wall in at least four directions.

In any aspect or embodiment herein, the particulate adsorbent has a length of about 1mm to about 20mm.

In any aspect or embodiment herein, the particulate adsorbent has a length of about 2mm to about 8mm.

In any aspect or embodiment herein, the particulate adsorbent has a retention of about 1.0g/dL or less.

In another aspect, the present disclosure provides a particulate adsorbent material produced by the methods of the present disclosure (i.e., methods of making the particulate adsorbent of the present disclosure).

While several embodiments of the present disclosure have been shown and described herein, it should be understood that these embodiments are provided by way of example only. Many changes, modifications and substitutions will now occur to those skilled in the art without departing from the spirit of the disclosure. Rather, the present disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the present disclosure as defined by the following appended claims and their legal equivalents. It is therefore intended that the specification and appended claims cover all such variations as fall within the spirit and scope of the disclosure.

The contents of all references, patents, pending patent applications and published patents cited in this application are expressly incorporated herein by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure herein. The following claims are intended to cover such equivalents. It should be understood that the detailed examples and embodiments described herein are given by way of illustration only and are in no way to be considered limiting of the present disclosure. Various modifications or changes thereto will suggest themselves to those skilled in the art and are intended to be included within the spirit and scope of the present application and be considered to be within the scope of the appended claims. For example, the relative amounts of the ingredients may be varied to optimize a desired effect, additional ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients. Other advantageous features and functions associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. In addition, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure herein. The following claims are intended to cover such equivalents.

Claims

1. A particulate adsorbent material for evaporative emission control, the material comprising:

an adsorbent having microscopic pores with a diameter of less than 100 nm;

macroscopic pores having a diameter of 100nm or more; and is also provided with

The ratio of the volume of the macroscopic pores to the volume of the microscopic pores is greater than 160%,

wherein the particulate adsorbent material has a retention of 1.0g/dL or less.

2. The particulate adsorbent material of claim 1, wherein the adsorbent has a retention of 0.75g/dL or less.

3. The particulate adsorbent material of claim 1, wherein the adsorbent has a retention of 0.25 to 1.00 g/dL.

4. A particulate adsorbent material according to any one of claims 1 to 3, wherein the adsorbent is at least one of activated carbon, carbon charcoal, molecular sieves, porous polymers, porous alumina, clay, porous silica, kaolin, zeolite, metal organic framework, titania, ceria or combinations thereof.

5. The particulate adsorbent material of any one of claims 1 to 4, wherein the adsorbent has a micropore volume as determined by BJH of 0.5cc/g or less or 225cc/L or less.

6. The particulate adsorbent material of any one of claims 1 to 5, wherein the adsorbent comprises a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

7. The particulate adsorbent material of any one of claims 1 to 6, wherein the particulate adsorbent material has a cross-sectional width of 1mm to 20 mm.

8. The particulate adsorbent material of claim 7, wherein the cross-sectional width is from 3mm to 7mm.

9. The particulate adsorbent material according to any one of claims 1 to 8, wherein the adsorbent has a hollow shape in cross section.

10. The particulate adsorbent material according to any one of claims 1 to 9, wherein the adsorbent comprises at least one cavity in fluid communication with an outer surface of the adsorbent.

11. The particulate adsorbent material according to any one of claims 1 to 10, wherein each portion of the adsorbent has a thickness of 0.1mm to 3.0 mm.

12. The particulate adsorption material of any one of claims 9 to 11, wherein at least one outer wall of the hollow shape has a thickness in the range of 0.1mm to 1.0 mm.

13. The particulate adsorption material of any one of claims 9 to 12, wherein the hollow shape has at least one inner wall extending between outer walls and having a thickness in the range of 0.1mm to 1.0 mm.

14. The particulate adsorption material of claim 13, wherein at least one of the inner wall, the outer wall, or a combination thereof has a thickness of 0.3mm to 0.8mm.

15. The particulate adsorption material of any one of claims 13 to 14, wherein at least one of the inner wall, the outer wall, or a combination thereof has a thickness of 0.4mm to 0.7mm.

16. The particulate adsorption material of any one of claims 13 to 15, wherein the inner wall extends outwardly from the hollow portion of the particulate adsorption material to the outer wall in at least two directions.

17. The particulate adsorption material of any one of claims 13 to 16, wherein the inner wall extends outwardly from the hollow portion of the particulate adsorption material to the outer wall in at least three directions.

18. The particulate adsorption material of any one of claims 13 to 17, wherein the inner wall extends outwardly from the hollow portion of the particulate adsorption material to the outer wall in at least four directions.

19. The particulate adsorbent material according to any one of claims 1 to 18, wherein the adsorbent has a length of 1mm to 20 mm.

20. The particulate adsorbent material of claim 19, wherein the length is from 2mm to 15mm.

21. The particulate adsorbent material of claim 19 or 20, wherein the length is from 3mm to 8mm.

22. The particulate adsorption material of any one of claims 4 to 21, wherein the activated carbon is derived from at least one material selected from the group consisting of wood, wood chips, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit pits, nut shells, nut pits, sawdust, palm, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof.

23. The particulate adsorption material of any one of claims 4 to 22, wherein the clay is at least one of a zeolite clay, bentonite, montmorillonite clay, illite clay, french green mud, paspalite clay, redmond clay, terramin clay, activated clay, fuller's earth clay, ormalite clay, vitalilite clay, rectorite clay, or a combination thereof.

24. The particulate adsorption material of any one of claims 1 to 23, further comprising at least one of:

a pore-forming material or processing aid that decomposes, dissolves, sublimates, evaporates or melts when heated to a temperature of 100 ℃ or more;

an adhesive;

a filler; or (b)

A combination thereof.

25. The particulate adsorption material of claim 24, wherein the pore forming material or processing aid is a cellulose derivative.

26. The particulate adsorption material of claim 24 or 25, wherein the pore forming material or processing aid is methylcellulose.

27. The particulate adsorption material of any one of claims 24 to 26, wherein the pore forming material or processing aid sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature in the range of 125 ℃ to 640 ℃.

28. A particulate adsorption material according to any one of claims 24 to 27, wherein the binder is a clay or silicate material.

29. The particulate adsorption material of claim 28, wherein the clay is at least one of a zeolite clay, bentonite, montmorillonite clay, illite clay, french green mud, paspalite clay, redmond clay, terramin clay, activated clay, fuller's earth clay, ormalite clay, vitalilite clay, rectorite clay, or a combination thereof.

30. The particulate adsorption material of any one of claims 1 to 29, wherein the packed bed of particulate adsorption material has a pressure drop of <40Pa/cm at an apparent linear air flow rate of 46 cm/s.

31. A method of making a particulate adsorbent, the method comprising:

mixing an adsorbent having microscopic pores with a diameter of less than 100nm with a pore-forming material or processing aid that sublimates, evaporates, chemically decomposes, dissolves or melts when heated to a temperature of 100 ℃ or more to form a mixture; and

heating the mixture to a temperature in the range of 100 ℃ to 1200 ℃ for 0.25 hours to 24 hours, forming macroscopic pores with a diameter of 100nm or more when the nuclear material sublimates, evaporates, chemically decomposes, dissolves or melts,

Wherein the particulate adsorbent has a ratio of the volume of the macroscopic pores to the volume of the microscopic pores of greater than 160%; and is also provided with

Wherein the particulate adsorbent material has a retention of 1.0g/dL or less.

32. The method of claim 31, further comprising extruding or compressing the mixture into a shaped structure.

33. The method of claim 31 or 32, wherein the adsorbent is at least one of activated carbon, molecular sieves, porous alumina, clay, porous silica, zeolite, metal organic framework, or a combination thereof.

34. The method of any one of claims 31-33, wherein the mixture further comprises a binder.

35. The method of claim 34, wherein the binder is at least one of clay, silicate, or a combination thereof.

36. The method of any one of claims 31-35, wherein the mixture further comprises a filler.

37. The method of any one of claims 31 to 36, wherein the particulate adsorbent has a cross-sectional width in the range of 1mm to 20 mm.

38. The method of any one of claims 31 to 37, wherein the particulate adsorbent comprises a body defining an outer surface and a three-dimensional low flow resistance shape or morphology.

39. The method of claim 38, wherein the three-dimensional low flow resistance shape or morphology is at least one of a substantially cylindrical, a substantially oval prism, a substantially sphere, a substantially cube, a substantially elliptical prism, a substantially rectangular prism, a lobed prism, a three-dimensional spiral or helix, or a combination thereof.

40. The method of any one of claims 31 to 39, wherein the particulate adsorbent comprises at least one cavity or channel in fluid communication with an outer surface of the particulate adsorbent.

41. The method of any one of claims 31 to 40, wherein the cross-section of the particulate adsorbent has a hollow shape.

42. The method of any one of claims 31 to 41, wherein each portion of the particulate adsorbent has a thickness of 0.1mm to 3.0 mm.

43. The method of claim 41 or 42, wherein the hollow-shaped outer wall has a thickness of 0.1mm to 1.0 mm.

44. The method of claim 43, wherein said hollow shape has at least one inner wall extending between said outer walls.

45. The method of claim 44, wherein the inner wall has a thickness of 0.1mm to 1.0 mm.

46. The method of claim 44 or 45, wherein at least one of the inner walls, at least one of the outer walls, or a combination thereof is 0.1mm to 0.8mm.

47. The method of any one of claims 44 to 46, wherein the inner wall extends outwardly from the interior volume to the outer wall in at least two directions.

48. The method of any one of claims 44 to 47, wherein the inner wall extends outwardly from the interior volume to the outer wall in at least three directions.

49. The method of any one of claims 44 to 48, wherein the inner wall extends outwardly from the interior volume to the outer wall in at least four directions.

50. The method of any one of claims 31 to 49, wherein the particulate adsorbent has a length of 1mm to 20 mm.

51. The method of claim 50, wherein the particulate adsorbent has a length in the range of 2mm to 8mm.

52. A particulate adsorbent material produced by the method of any one of claims 31 to 51.